Friction particle for brake lining

ABSTRACT

A friction particle, useful in applications where cashew nut shell oil friction particles have been used, may be prepared by the reaction at a temperature from about 225* to about 400* Fahrenheit of a non-oxyalkylated resole with resin selected from the group consisting of an oxyalkylated resole, an alkylated resole, an alkylated novolac, an oxyalkylated novolac, and mixtures thereof until it is insoluble, infusible, and does not soften slightly under mechanical force at temperatures below about 400*F, and has substantially no cohesive or bonding strength.

United States Patent 1191 Grazen et al. Feb. 4, 1975 15 FRICTION PARTICLE FOR BRAKE LINING 2,510,513 10/1951 Bloch .1 260/838 1 1 Frank Gwen; Melvin B11119; 333122 171322 li'lliZZ/Jiiiiii........ 33:31:31 5231233 Frank Bryzmsky, all of North 3,549,576 12/1970 Anderson et al. 260/838 Tonawanda, N.Y. 3,658,751 4/1972 Grazen et al. 260/838 [73] Assignee: Hooker Chemicals & Plastics C0rp.,

Niagara Falls, NY, Primary ExaminerJohn C. Bleutge Filed: Dec. 1972 filtlojrgey, Agent, or FIrm-Peter F. Casella, James F. [21] Appl. No.: 318,950

Related US. Application Data [57] ABSTRACT Division 981 1 19711 A friction particle, useful in applications where cag g g g g g g gg shew nut shell oil friction particles have been used, may be prepared by the reaction at a temperature from about 225 to about 400 Fahrenheit of a nonl52] 02 '2 oxyalkylated resole with resin selected from the group.

260/838 260/840 260/1); consisting of an oxyalkylated resole, an alkylated re- [511 I t Cl C08 slllo sole, an alkylated novolac, an oxyalkylated novolac, [58] 38 S 39 and mixtures thereof until it is insoluble, infusible, and 0 are does not soften slightly under mechanical force at temperatures below about 400F, and has substantially [56] References Cited no cohesive or bonding strength.

UNITED STATES PATENTS 2,351,716 6/1944 Smith 260/838 7 Clam, N0 Drawmgs 1 FRICTION PARTICLE FOR BRAKE LINING This is a division of co-pending application Ser. No. 188,598, filed Oct. 12, 1971, now U.S. Pat. No. 3,781,241 issued Dec. 25, 1973, which is a division of application Ser. No. 872,753, filed Oct. 30, 1969, now U.S. Pat. No. 3,658,751.

This invention relates to novel cured phenolic resins to be used as a friction particle material. It is especially useful where cashew nut shell oil friction particles, called Cardolite", have been used in the past.

Phenol aldehyde, or hydroxy aromatic-aldehyde condensation products having methylol side or end groups are known in the art as resoles. They are formed from condensing a phenol with an excess of aldehyde and with an alkaline catalyst, also known as onestage" resins and are of the thermosetting type. Except when oxyalkylated, they are self-setting. That is, upon the application of heat there results the formation of a resite", which is an infusible three-dimensional polymer.

Novolac phenol aldehyde resins, on the other hand, are phenol-ended chain polymers. They are formed by the reaction of an aldehyde with an excess of phenol in the presence of an acid catalyst and/or heat. They are thermoplastic, permanently soluble and fusible. However, upon the addition of a curing agent, they can be cured into an insoluble, infusible resin. Thus, novolac resins are known as two-stage resins.

Phenol aldehyde condensation products have been used as binders for abrasive materials. However, to our knowledge, the novel cured phenol aldehyde products of this invention have not been used as a friction particle per se.

As used herein friction particle is intended to means having the properties of substantially no soften ing at elevated temperatures and will not flow together or cohere with other particles, as a friction binder" would, or fuse with like friction particles. It is insoluble, having an acetone extraction of less than 35 percent and often less than 5 percent; it is infusible, i.e., has gone beyond the B stage, to the C" stage. It will not melt at 700 F. A friction particle is held in place with a friction binder.

As used herein, a friction binder has the properties of flowability, and had adhesive and cohesive bonding action and thereby binds together the asbestos and other additives (including a friction particle) necessary for building a brake lining or other similar article of manufacture. The binder, as supplied to the industry, will melt as a dry powder or is a liquid resin, and can be either an A stage or B stage resin. The binder becomes a C stage resin after it is combined with the other ingredients and cured.

This composition of the binder, friction particle and other additives, is heated to about 300400 F. and pressed at about 500-2000 pounds per square inch in order to form a brake lining composition, or clutch facing or other braking device. Thus, the friction particle is substantially insoluble and infusible, softening only at elevated temperatures (i.e., above about 400-500 F.).

1t has now been found that a composition of matter useful as a friction particle can be prepared by the reaction at a temperature from about 225 to about 400 F. of a non-oxyalkylated hydroxy aromatic hydrocarbonaldehyde resole with a resin selected from the group consisting of an oxyalkylated hydroxy aromatic hydrocarbon-aldehyde resole, an alkylated hydroxy aromatic hydrocarbon-aldehyde resole,an alkylated hydroxy aromatic hydrocarbon-aldehyde novolac, an oxyalkylated hydroxy aromatic hydrocarbon-aldehyde novolac, and mixtures thereof, until it is insoluble, infusible, and does not soften slightly under mechanical force, such as a spatula, at temperatures below about 400 F., and has substantially no cohesive or bonding action or strength. The crude material is initially in lump form. which is then ground to the size specification of the customer. The first said resole can be alkylated but not oxyalkylated. Among the preferred embodiments of this invention are the following:

1. The reaction product of between about 5 and about 40 percent by weight of an oxyalkylated resole with between about 95 and about 60 percent by weight of one or more of a. one or more non-oxyalkylated, non-alkylated resoles,

b. a non-oxyalkylated, alkylated resole,

c. a mixture of a non-oxyalkylated alkylated resole and a non-oxyalkylated, non-alkylated resole,

d. a mixture of a non-oxyalkylated, non-alkylated resole and a non-oxyalkylated alkylated novolac, and

e. a mixture of a non-oxyalkylated, non-alkylated novolac and a non-oxyalkylated, non-alkylated resole.

2. The reaction product of between about 95 and about 60 percent by weight ofa non-oxyalkylated, nonalkylated resole with between about 5 and about 40 percent by weight of one or more of a. an oxyalkylated novolac, and

b. a non-oxyalkylated, alkylated resole.

3. The reaction product of between about 5 and about 40 percent by weight of an oxyalkylated novolac with between about 95 and about 60 percent by weight of one or more of a. two or more non-oxyalkylated, non-alkylated resoles,

b. an alkylated resole.

c. a mixture of an alkylated resole and a nonoxyalkylated, non-alkylated resole,

d. a mixture of a non-oxyalkylated, non-alkylated resole and a non-oxyalkylated alkylated novolac, and

e. a mixture of a non-oxyalkylated, non-alkylated resole and a non-oxyalkylated, non-alkylated novolac.

4. The reaction product of between about 5 and about 95 percent by weight of a solid, B-stage nonoxyalkylated, alkylated resole, with between about 95 percent and about 5 percent by weight of a liquid, A- stage, non-oxyalkylated, alkylated resole.

5. The reaction product of between about and about percent by weight of a non-oxyalkylated, alkylated resole, with between about 30 and about 10 percent by weight of a non-oxyalkylated, alkylated novolac.

6. The reaction product of between about 5 and about 50 percent by weight of a non-oxyalkylated, alkylated resole, with between about 5 and about 30 percent by weight of a non-oxyalkylated, alkylated novo lac, and with between about 25 and about 90 percent by weight of a non-oxyalkylated, non-alkylated resole.

In general. an oxyalkylated hydroxy aromatic material, whether it is a novolac or a resole, will not react with a novolac by itself. The methylol groups on a resole are believed to be needed to react with the polyol groups of the oxyalkylated materials.

The friction particle is formed by blending and reacting the resole with the novolac, or oxyalkylated resole. Usually, the resole and oxyalkylated resole or oxyalkylated novolac are both liquids, so blending is easily achieved. However, when one is a solid, it is powdered and mixed with the liquid. When both are solids, both are dry blended such as by ball milling together. Then they are mechanically blended, such as by being passed through a hammer mill equipped with a quarter mesh screen. I

Following blending, the resins are heated to about 225 F. to about 400 F., and preferably from about 325 F to about 375 F., until a resin of friction particle consistency is formed.

Examples of phenols which can be used in preparing a phenol aldehyde resole or novolac for use in practicing the invention include ortho-, paradirecting hydroxy or amino aromatic compounds having 6 to 24 carbon atoms such as phenol itself (C H OH), naphthol, anthranol and substituted derivatives thereof where the substituents'on the aromatic compound are independentlyselected from H, Cl, Br, F, NH, and

a. alkyl groups or radicals of l to 60 carbon atoms, preferably of l to 30 carbon atoms, and their various isomeric forms and substituted on the aromatic nucleus in the ortho or para position;

b. cycloalkyl groups of 5 to 12 carbon atoms such cyclohexyl, cyclopentyl, methylcyclohexyl, butylcyclohexyl, and so forth;

c. alkyl, aryl, and cycloalkyl ketonic groups wherein the hydrocarbon portion is as defined above in (a) and (b);

(1. alkyl, aryl and cycloalkyl carboxylic groups wherein the hydrocarbon part is defined asabove in (a) and (b);

e. aryl groups of 6 to 24 carbon atoms such as phenyl, naphthyl. anthryl, and the like;

f. aryl substituted alkyl wherein the aryl is phenyl which may contain lower alkyl and/or hydroxy substituents so that the resulting hydroxy aromatic is, for example, a bisphenol; and

g. mixtures of the aforesaid hydroxy aromatics.

Suitable substituted phenols include the following: para-phenyl phenol, para-benzyl phenol, para-betanaphthyl phenol, cetyl phenol, para-cumyl-phenol, para-tert-butyl phenol, sec-butyl phenol, para-tertamyl phenol, para-tert-hexyl phenol, para-alphanaphthyl phenol, para-hydroxyacetophenone, parahydroxybenzophenone, para-isooctyl phenol, para-tertoctyl phenol, paracyclohexyl phenol, para-d-limonene phenol, para-l-limonene phenol, a phenol alkylated with oleic acid, such as phenol alkylated with oleic acid, para-decyl phenol, para-dodecyl phenol, paratert-decyl phenol, butyl naphthol, amyl anthranol, para-nonyl phenol, para-methyl phenol, bisphenols such as para,para-isopropylidene diphenol, para,paramethylene diphenol, as well as the corresponding ortho-derivatives of the previously mentioned comounds such as ortho-butyl phenol and ortho-nonyl phenol as well as mixtures thereof, and aniline.

Mixtures of various hydroxy aromatic compounds mentioned herein also may be used.

Included among the phenolic reactants which may be used are those known as the cresylic acids and these often comprise a heterogeneous mixture of having two 4 reacting hydrogen positions on each of them; that is, compounds unsubstituted in the orthoand paraposi tions of the molecule, to compounds that only have one functional position, and hence, relatively unreactive. These compounds may include the following: 3,5- xylenol, m-cresol, 3,4-xylenol, 2,5-xylenol, 2,3-xylenol, phenol, p-cresol, ortho-cresol, 2,4-xylenol, and 2,6- xylenol. Cresylic acids or tar acids aregenerally applied to phenol and its homologs which may include cresols, xylenols, trimethyl phenols, ethyl phenols, and higher boiling materials such as dihydroxy phenols, polycyclic phenols and the like. They are often obtained by a lowtemperature trimerization of coal, lignite, and the like, or a conventional high-temperature coke oven tar. or the liquid product of petroleum cracking both thermo and catalytic, shell oil, coal hydric hydrogenation products, and the like.

Polyhydroxy aromatic reactants, such as resorcinol, may also be used.

Particularly useful in this invention are mixtures of aniline and phenol to react with an aldehyde or ketone to produce either a novolac or a resole, depending on the other conditions described above.

Also useful in the invention are mixtures of urea and phenol to react with the aldehyde or ketone to produce either a novolac or a resole depending on the other condition described above.

Among the aldehydes which may be used within the scope of this invention to produce either the resole or the novolac, are formaldehyde or any of its variations, such as 37 percent formalin concentration or paraaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, isopentaldehyde, and the like. The aldehyde should have not more than 8 carbon ,atoms and should not detrimentally affect the resinification or oxyalkylation of theresin. Preferred aldehydes are those having from 1 to 4 carbon atoms, such as formaldehyde, which may be in aqueous solution (37 percent), or in any of its low polymeric forms such as paraform or trioxane. Other aldehydes include para-aldehydes, furfural, 2- ethyl-hexanal, ethylbutyraldehyde, heptaldehyde and glyoxal, benzaldehyde and crotonaldehyde.

Novolacs To prepare a novolac, the proportion of aldehyde to be condensed with the hydroxy aromatic compound may be varied in order to obtain different molecular weights, and the viscosity of the finished resin may be controlled by the mole weight of the novolac; preferably the proportion of aldehyde employed is from 0.5 to 1.0 per mole of the hydroxy aromatic compound.

Among the substituted phenols which may be used to prepare the novolacs for this invention are those substituted with long-chain ethylenically unsaturated hydrocarbons, such as the linseed-type oils. However, it is within the scope of this invention to employ any animal and/or vegetable oil which achieves the objects of this invention based on the similarity in properties with the long-chain hydrocarbon oils. Such oils would be positioned on the phenol in the orthoor parapositions, and preferably in the paraposition. Many of them are similar in properties to linseed oil having nonconjugated unsaturation of at least 50 iodine number, and have sufficient compatibility with the novolac after it is polymerized. Safflower oil is typical of these oils. It may be in the form of a glycdrol ester of the fatty acids wherein the fatty acids are of a composition comprising more than 40 percent by weight of linolenic acid. The remaining percentages of fatty acid can be any saturated or ethylenically unsaturated fatty acid having 12 to 22 carbon atoms and more preferably oleic and linolenic acid so that the fatty esters have an iodine number of at least 50. The iodine value (iodine number) is a measure of unsaturation, and is defined as the number of grams of iodine required per 100 grams of unsaturated material to obtain the saturated material. In addition to the preferred glycerol ester, other polyhydric alcohols can be reacted with the described fatty acids to produce a low acid number ester of a polyol having 2 or more hydroxyl groups. Typical polyols include ethylene glycol, diethylene glycol, pentaerylthritol, dipentaerythritol, sorbitol and the other polyhydric alcohols.

The acid catalyst to be used when preparing the novolacs to be used in this invention may be chosen from oxalic acid, sulfuric acid, hydrochloric acid and other strong acids used in the art for preparing novolacs. In addition, wetting agents of the anionic type, such as sodium alkylaryl sulfonates, are also useful as secondary catalysts in preparing novolacs.

The two-stage resins are curable by reaction with hexamethylene tetramine to form dibenzyl and tribenzyl amines, as well as hexatriphenol. One may also use ammonium hydroxide, which reacts with the formaldehyde to form hexamethylene tetramine. Other amines may also be used, such as ethylene diamine or ethylene triamine, or methylamines, etc. These can be used to react with formaldehyde to form a composition similar to hexamethylene tetramine. The resulting compound would be an aldehyde donor.

The phenol aldehyde. novolac type resin is prepared by charging the desired phenol and aldehyde raw materials and catalysts to a reaction vessel. The reaction be gins at about 100 C. and proceeds under temperatures up to about 200 C., at any pressure up to about 100 lbs/square inch gauge for about 1 /2 hours, or until the desired degree of polymerization has taken place. Thereafter, the catalyst is neutralized where necessary, and the excess reactant, water, and other materials are taken off by dehydration and the molten resin is discharged from the vessel. It has been found that a novolac which has not been neutralized and is stable will cure more rapidly with a resole than a novolac which has been neutralized.

From the foregoing, it is apparent that many hydroxy aromatic compounds may be used in practicing the present invention to provide a novolac which can be then reacted with an hydroxy aromatic aldehyde resole to form the friction particle of this invention, provided the aromatic hydroxyl group is reactive and the hydroxy aromatic compound is capable of reacting with an aldehyde or a mixture of aldehydes to produce a novolac condensate. Pure, refined phenols may be used, but this is not necessary. For instance, phenols may be alkylated and then may be reacted in crude form with an aldehyde. In such crude form, the phenols may contain some polyalkylated, as well as non-alkylated, phenols.

The process for alkylation of a phenol is well-known in the art. First, dehydration (of water) is carried out with vacuum at elevated temperatures, for instance, between about 100 and about 150 C. under a vacuum of between about 20 and about 30 inches of mercury. Then, the dehydrated phenolic material is acidified to a pH of between about 1 and about 5 with H2804 or in some cases BF Following this, a terpene or vegetable oil is added and the reaction mixture heated to between about 80 and about 140 C. at atmospheric pressure. The molar ratio of reactants is between about 0.1 mole of terpene or vegetable oil per mole of phenol to about 2.5 mole ofterpene or vegetable oil per mole of phenol. When tung oil is employed as a vegetable oil in the alkylation, use of BF to acidify would cause gelation, so it is not used, but H 80 can be used.

The proportion of aldehyde to be condensed with the hydroxy aromatic compound to form a precondensate may be varied to prepare novolacs ofdifferent molecular weights. Viscosity of the finished precondensate may be controlled by the mole weight of the novolac. Preferably, the proportion ofaldehyde employed varies from about 0.5 to 1.0 mole per mole of phenol when a monoor difunctional phenol is used. In instances where a trifunctional phenol is used, i.e., unsubstituted in the orthoand parapositions, a preferred upper limit of the aldehyde may be about 0.70 mole of aldehyde per mole of phenol so as to minimize the formation of insoluble, infusible condensates. It is preferred that the aldehyde and phenol be condensed using an acid catalyst to shorten the time required for complete condensation of the reactants. Suitable acid catalysts include sulfuric acid, hydrochloric acid, and oxalic acid. These catalysts are generally employed in the amount of 0.1 to about 5 percent by weight of phenol to be condensed.

Where a mixed aldehyde, phenolaldehyde precondensate is to be prepared, it is formulated by charging the desired phenol and aldehyde raw materials and catalysts to a reaction vessel. The reaction proceeds under temperatures from about 25 to about 150 C. at a pressure from about ambient up to about 100 pounds per square inch gauge pressure for a period of time from about 5 minutes to about 5 hours, a'suitable time being about one and one-half hours, or until the desired degree of condensation has taken place. The phenol is first reacted with the longer-chain aldehyde to form a phenol-longer chain aldehyde precondensate, followed by a second-step reaction of the phenol-longer chain aldehyde precondensate with formaldehyde to form a thermosettable phenol aldehyde precondensate material. 1n the second step, the reactants are refluxed at at mospheric pressure, although higher reflux temperatures up to about 150 C. can be used by employing elevated pressure. The formaldehyde can be added all at once in the second step, or added gradually. 1f the formaldehyde is added all at once, then a temperature range between about 50 and about 60 C. is used at the beginning of the second-step reaction, until the exothermic reaction subsides, and then the temperature is increased slowly to between about and about C. and held until further exothermic reaction subsides, and then the reaction mixture is heated to reflux temperature which is about C. at atmospheric pressure. If elevated pressure is used, then the reflux temperatures can be increased to as high as about degrees centigrade. 1f the formaldehyde is added gradually in the second step, then a temperature range between about 95 and about 140 C. can be used. The catalyst is then neutralized and the excess reactant, water and other materials are taken off.

While the precondensate is still at an elevated temperature, from about 25 to about C., but below factor is the resulting viscosity of the precondensate.

prepared, rather than the actual volume of solvent charged. Among the solvents which may be used for this purpose are ethanol, methanol, toluene, xylene. ketones, such as acetone, and methylethyl ketone, and mixtures of aromatic and aliphatic hydrocarbons, such as mixtures of benzene and mineral spirits, or benzene and acetone.

Oxyalkylation Oxyalkylated resins are prepared which preferably contain substantially no free reactive hydroxy aromatic groups, for example, less than about 0.5 percent of the aromatic hydroxy] present originally in the hydroxy aromatic or hydroxy aromatic aldehyde condensate. To remove the aromatic hydroxys, the hydroxy aromatic aldehyde resin can be reacted with a compound which etherifies the aromatic hydroxy groups so that almost all of the aromatic hydroxy groups present in each hydroxy aromatic aldehyde condensate unit are so reacted.

The preferred method of hydroxyalkylation is by reaction with compounds containing a mono-oxirane ring. .Such compounds include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and cyclohexene oxide, glycidol and epichlorohydrin. Many other monoepoxides can be used, but the alkylene oxides containing not more than 6 carbons are generally preferred. Additional useful compounds are phenyl glycidyl ether and related compounds prepared from the reaction of epichlorohydrin and monofunctional alkylated and halogenated phenols such as pentachlorophenyl glycidyl ether.

Catalysts for the reaction of the oxirane ring compounds and pehnolic hydroxy groups may be alkali or alkaline earth hydroxides, primary amines, secondary amines, tertiary amines or basic alkali salts. These include sodium, potassium, lithium, calcium and barium hydroxides, amines such as methyl, dimethyl, diethyl, trimethyl, triethyl, tripropyl, dimethyl benzyl, dimethyl hydroxyethyl, dimethyl-Z-hydroxypropyl and the like, and salts of strong bases and weak acids such as sodium acetate and benzoate.

The reaction may be carried out at temperatures of about room temperature to 250 C., and preferably in the absence of solvents, although solvents may be used to reduce viscosity when desired. When oxyalkylating resoles, the reaction should be carried out at lower temperatures than when oxyalkylating novolacs, because there is a possibility that reaction ofthe methylol groups with other methylol groups gives methylene linkages, formaldehyde and gelation. When oxyalkylating a novolac, temperatures between room temperature and about 200 C. can be used. When oxyalkylating a resole, temperatures between room temperature and about 100 degrees Centigrade may be used.

The aromatic hydroxy] of the novolacs may also be hydroxyalkylated by reacting alkylene halohydrins with the aromatic hydroxyl using equivalent amounts of an alkali metal hydroxide to bring about the reaction. Suitable alkylene halohydrins are ethylene chloroand bromohydrins, propylene chloroand bromohydrins, 2,3- butylene chloroand bromohydrins, and glyceryl chloroand bromohydrins.

Another method for hydroxylalkylating novolacs is reaction with alkylene carbonates such as ethylene carbonate and propylene carbonate. using a catalyst such as potassium carbonate.

At least one mole ofalkylene oxide or other etherifying or esterifying agent is required per mole of aromatic hydroxyl. However, resins prepared by reaction with up to 7 moles of alkylene oxides per mole of phenolic hydroxyl have been found to be useful.

Resoles is desirable. The reaction mixture is then cooled and the catalyst neutralized with some acid such as glacial acetic acid and the pH is adjusted to roughly 6 to 75. The reaction mixture may be then further reacted with hexamethylene tetramine or some other aldehyde donor, i.e., curing agent. The resin is then dehydrated to between about 50 to 95 percent solids, and preferably between about 8| to percent solids.

The alkaline catalyst used in preparing the resoles to be used in this invention may be any of those known in the art; for instance, sodium hydroxide and calcium hydroxide. In general, the alkali metal hydroxides and the alkaline earth metal hydroxides and ammonium hydroxide and the amines such as triethanol amines may be used.

Following the intercondensation reaction to form a resole, a stoichiometric quantity of a strong acid such as sulfuric acid, hydrochloric acid, phosphoric acid or oxalic acid, or the like, is added to the reaction mixture in order to neutralize the alkaline condensation catalyst. Sulfuric acid is conveniently employed to neutralize a sodium hydroxide catalyst. The alkaline catalyst may also be neutralized by dilution through repeated washing, however, it is preferred to use an acid. The final resin should have a pH between about 5.5 and 7.5 for good stability.

The hydroxy aromatic compound employed in a resole can be alkylated, if desired, with alkyl groups consisting' l to 12 carbon atoms, or with unsaturated groups, including the long-chain unsaturated vegetable or animal oils, to form alkylated hydroxy aromatic compounds that when reacted with an aldehyde form heat reactive" resoles. These include alkylene groups of 2 to 36 carbon atoms, fatty acids, polyethers, alkyl ethers, polyesters and polyols and mixtures of these.

Among the high molecular weight or polymeric materials containing aliphatic carbon-to-carbon unsaturation, there are included such naturally occurring materials as unsaturated vegetable, fish or animal oils such as linseed, soya, tung, sesame, sunflower, cotton seed, herring, menhaden, and sardine oils, etc., or chemically modified naturally occurring materials such as allyl.

ethers of starch, cellulose or acrylate esters thereof, etc., synthetic drying oils, polymers obtained by polyetherification of such unsaturated compounds such as maleic, fumaric, itaconic, aconitic, chloromaleic, di-

merized fatty acids, anhydrides or acids from allyl glycerol, methallyl glycerol ether, glycerol monoacrylate, butene diol, pentene diol. or polymers obtained by polyetherification of the unsaturated polyols. Other oils include castor oil, tall oil, oiticica oil, safflower oil, and the like, oleic and linolenic acids. These fatty acids have from 12 to 22 carbon atoms. They are often in combination as a glycerol ester or in combination with other polyhydric alcohols or polyols such as ethylene glycol, diethylene glycol, pentaerythritol, dipentaerythritol, sorbitol, and the like polyhydric alcohols.

The blending and reacting of the resole with the other components in accordance with this invention may be in various proportions, depending upon the ultimate properties desired in the friction particle to be produced, but will generally be in the range of from about 60 to about 95 weight percent of the nonoxyalkylated resole based on the total weight of resin components.

It is to be understood that the oxyalkylated resole or oxyalkylated novolac described herein will not be a friction particle alone unless reacted with a nonoxyalkylated, non-alkylated resole resin or with a nonoxyalkylated, alkylated resole resin. The oxyalkylated resole product is a liquid and will not cure. The preferred compositions of the invention contain at least one of an oxyalkylated resole and an oxyalkylated novolac in combination with the non-oxyalkylated resole.

The friction particle of this invention may be used alone or with other friction materials known in the art. A typical friction element contains about 30 to 60 weight percent asbestosfiber, up to 40 weight percent other inorganic filler and abrasives, about 5 to l5 weight percent organic filler, including the particle of this invention, and about 15 to 30 weight percent binder; all percents are by weight of total composition. Asbestos fiber, other abrasive materials and filler materials are charged into a mixer followed by the addition of a binder, such as a varnish material. The materials are kneaded until the fiber, abrasives, and any fillers are thoroughly wetted and a uniform mass is obtained. The mass is discharged from the mixer, rolled out into sheets or extruded or pressure molded and dried, after which it is ready for further processing into friction elements.

The abrasives, that is, the friction imparting agents and fillers, which may be used in addition to the abrasive material disclosed and claimed herein, within the scope of this invention include, but are not limited to brass chips, metal shavings and filings, silica, talc, wood flour, chalk, clay, mica, fiber glass, felt, carbon black, graphite, metal nitrides and oxides, and ground cashew nut shell oil polymerizate. These abrasives and fillers may be used in addition to the friction particle of this invention to achieve the particular amount of bulk and coefficient of friction desired. Some consumer specification specify that the friction particle should be 90 percent finer than mesh and coarser than 100 mesh. Other consumer specifications call for coarser or finer friction particles.

The following examples are given to further illustrate the invention. Unless otherwise indicated, all parts are by weight and temperatures in degrees centigrade.

EXAMPLE 1 PART A (The Resole)- A reaction vessel is charged with l00 parts of phenol, 5 parts of cresylic acid, 1 10 parts of formalin (37 percent formaldehyde) and 1.0 parts of flake caustic dissolved in 4 parts of water. This reaction mixture is heated gradually to reflux and held at reflux to less than 5 percent free formaldehyde and cooled to C., after which 1.5 parts of glacial acetic acid is added which neutralizes this composition to a pH of 6.8-7.2. After the pH range is achieved the resin is dehydrated to 81-85 percent solids and cooled to room temperature. The resultant product is a viscous liquid, and is identifled as resin Ra in Table V.

PART B (The Oxyalkylated Novolac) The oxyalkylated novolac may also be referred to as a polyol of a novolac which is oxyethylated, using from about one mole to about 7 moles of ethylene oxide to 1 mole of phenol, depending on the properties desired. For this Example, a resin was used with a ratio of 2 moles of ethylene oxide is one mole of phenol.

A typical modified phenol-aldehyde condensation product is prepared by introducing 3,000 parts phenol, 13 parts of'oxalic acid catalyst and 6 parts of a wetting agent of Nacconol (sodium alkylaryl sulfonate) into a jacketed reactor and heating to C. (The anionic wetting agents of alkylaryl sulfonate type are preferred.) Then 1,1 10 parts of a 37 percent aqueous formaldehyde solution are added to the reactor at a rate that the heat of reaction provides a vigorous reflux. Refluxing is continued for 2 hours after the completion of the formalin addition. The reactor contents are dehydrated at C. and then dephenolated at 200 C. at 50 millimeters vacuum. Approximately 2,030 parts of phenol-aldehyde condensate are produced. Then 7.2 parts of sodium hydroxide are introduced to the reactor. Ethylene oxide is then added to the reactor as either a vapor or a liquid. The reactor temperature is maintained at l90 C. for the initial 2 hours and is then permitted to increase to the range of 200 to 220 C. until the addition of 878 parts of ethylene oxide is complete. The resulting condensation product had a hydroxyl number of 370, and a Gardner viscosity at 50 C. of about 2,000 seconds, and is resin Nf in Table VI.

The novel friction particle is made by blending 60 parts of Part A with 40 parts of Part B, curing 8-l6 hours at 325 to 375 F., grinding to the desired screen size necessary for a friction particle useful in the arts. In this particular Example, the blend was cured for 16 hours at 350 F. and ground to 20 mesh. The resulting particle was made up into a brake lining, tested by standard procedures and found to be satisfactory for this use.

EXAMPLE 2 70 parts of Part A and 30 parts of Part B of Example l were blended and reacted, using the same curing cycle as in Example I. The resulting product was ground to 20 mesh and found to be superior to a polymerized cashew nut shell oil friction particle known as Cardolite in the trade, having softening properties at 500 F. when compressed slightly with an 8 inch spatula (5/8 wide by 4 long by l/32 inch thick blade). Also the heat loss at 700 F. was lower than that of Cardolite.

EXAMPLE 3 80 parts of Part A and 20 parts of Part B of Example 1 were blended and reacted, using the same curing cycle as in Example 1. The resulting product was remove solvents and other volatiles. The linings were then cut to proper length, reheated for 2 to 3 minutes at about 163 centigrade, bent or arched to the desired curvature and placed into form (i.e., molds) for curing.

. 1 2 ground to 20 mesh and had properties similar to those 5 These lmmgb l Cured 8 hours about C. The cured lmmgs after cooling were expanded to the of the product of Example 2. f b k h Th l The particles obtained in the above Examples 1. 2 P g f 5,126 mourvmng j e f d: and 3 were superior to friction particles made from pomg 8 El wkere m e bmbtlcmll ml lymerized cashew nut shell oil commonly called Cardom use on automo e M lite, presently used as friction particles in the brakelining industry. The particles made in accordance with the invention are less subject to migration of components EXAMPLES which results in brake linings with better *fade" characteristics. The particles of the invention are more heat '5 in Table 1, Examples 5-12 are shown in tabular form. resistant and can be made with more uniform quality, In each ofthese Examples (except Examples 10, 1 1 and with better control of end properties. The particles are 12) the resins were weighed into a beaker and mechanless toxic to the skin than Cardolite, which has the furically mixed. The mix was spread into aluminum pans ther disadvantage of being solely available from foreign (2 /2 inches by 7 inches) and cured in an air-circulating sources. The products of the in ention Can also be 20 oven at the specified temperature and time. The formumade at lower cost. lations for the resoles and novolacs used are given in Tables V and V], respectively. Example is a repeat EXAMPLE 4 of Example 2. in Example 11, a Cardolite NC-104-2O The friction particle (7 parts) of Example 1 was used sample of cashew nut shell oil friction particles is given in formulatinga mixture'comprising 62.37 parts of Dry 25 for comparison purposes. In Example 12, since both Mix, 0.63 part of hexamethylenetetramine, 16.4 parts resins are liquids, the materials were mixed in a galof varnish, parts of rubber solvent (mainly, mineral lon kettle. in all other respects, however, the procespirits) and 0.6 part water. The Dry Mix is composed dares and equipment were the same as the other Examof 93 parts by weight of asbestos shorts, Quebec Stanples in Table I.

TABLE 1 Example Weight Cure Cure Volatile Acetone Hot Plate Behavior at Number Resole Novolac Ratio Temp. Time Loss Extractablc 500F Spatula Test Resin Resin Resole/ Wt. Formula Wt. Formula Novolac C Hrs. 72 71 5 195 Re 15 Na 90/10 175 16 1 1.93 2.07 Smoky, softens slightly under spatula pressure 6* 195 Re 15 Na 90/10 175 16 14.3 3.14 Smoky, softens slightly under spatula pressure 7 225 Rf 15 Na 90/10 175 16 22.7 13.66 Very smoky, softens slightly,

' color change 8 162 Re Nd /30 175 16 13.6 25.61 Smoky, changes to a wet, oily mess Soft 9 225 Rf 15 Nd /10 175 16 17.9 11.52 Smoky, softens slightl 10 140 Ra 60 Nf 70/30 16 24.9 21.65 Smoky. very slight so tening. color change 1 1 Cardolite NC-104-20 Cashew Nut Shell Oil Friction Particles 25.9 2.59 Very smoky, softens slightly,

oily odor, particle breakdown 12 Rg 60 Nf 70/30 120 22 17.27 3.63 Smoky, slight softening, color change 2.4 grams of hexamethylenc-tetramine were also added into the mix.

Notes: Weights are in grams Volatile loss is at 700F for one hour Acetone extractable test is ASTM D-494-46 All materials tested were ground through 20 mesh Ratio is of resin solid content dard Asbestos Grade 7K, and 7 parts by weight of the friction particles. The moisture content of the Dry Mix is held low between 0.75 and 1.0 percent to avoid any possibility of blistering of the element during cure.

To an internal mixer equipped with a Sigma-type blade were charged the Dry Mix and hexamethylenetetramine. The dry materials were mixed and blended for 5 minutes. Then the varnish and toluene were added and mixed for 1 hour until the mass was uniform. The dough-like mix was then discharged from the mixer and charged to an extruder. The extruder is equipped with a 2 inchby A inch rectangular die and has an applied ram pressure of 100 to 300 pounds per square inch. The dough-like mix was then extruded in a shape which was satisfactory for brake linings. The extruded linings were oven dried for 3 hours and with a gradual increase of temperature up to about 88C. to

EXAMPLES 15-27 In Table 11, Examples 15-27 are shown in tubular form. The procedure used is set forth in the footnote of Table 11. The formulations for the resoles and novolacs used are given in Tables V and V], respectively.

TABLE 11 Example Resole Novolac Ratio Volatile Acetone Hot Plate Behavior at Number Formulation Formulation Resole/Novolac Loss. Extractable, 7: 500F Spatula Test 15 Kg 7.51 0.0 No smoking or softening- 16 Rat 6.29 0.0 No smoking or softening 17 Re Nf 70/30 36.72 2.29 Slight softening-slight smoking 18 Re 6t Rd M 70/30 25.92 3.70 Slight softening-no smoking 19 Rg Ng 70/30 8.17 0.03 No smoking or softening 20 Ra Ng 70/30 10.23 1.68 Slight softening 21 Rg Nh 80/20 7.23 0.0 Slight softening 22 Ra Nh 80/20 7.00 0.18 Slight softening 23 Rg Ne 70/30 6.60 0.67 Slight smoking, no softening 24 Re Hycar 1561 90/10 9.35 0.49 Very smoky, melts and turns Rubbery Latex 25 Rb & Rc Nf /30 18.35 0.58 No smoking, no softening 26 Rg Ne /20 7.0 4.34 Slight smoking, slight softening 27 Ra Nc 70/30 6.45 0.60 Slight smoking, no softening Notes: All components were weighed into a beaker (200 grams total mix) and mechanically mixed. The mix was spread into aluminum pans (2%" an air circulation oven at 175C for 16 hours. Acetone extractable test is ASTM D-494-46 Volatile loss is at 700F for one hour All materials were ground through 20 mesh EXAMPLES 28-46 x 7") and cured in permitting more flexibility in the supply of friction particle products to the industry.

EXAMPLES 47-62 In Table IV, Examples 47-62 are shown in tabular form. They are presented to further illustrate the variation in resoles and novolacs which can be employed to produce a friction particle. The procedure used was the same as that in Examples 5-9 of Table 1.

TABLE 111 VARIATIONS ON EXAMPLES 12 AND 14 IN TABLE 1 4 Cure Cure Volatile Acetone Ex. Resole Novolac Time Temp. Loss, Extractable, No. Formulation Formulation Ratio Hours C 71 7: Comments 28 Ra Nf 70/30 1 200 9.4 23.58 Mixed under vacuum while heating from C to C. Hot plate cure 59 sec. 29 Ra Nf 70/30 16 21.4 28.59 Mixed under vacuum while heating from 85C to 105C.

Hot plate cure 72/77 sec. 30 Ra Nf 60/40 16 120 16.96 41.8 Mixed under vacuum while heating from 85C to 90C. Hot plate cure 101/106 sec. 31 Ra Nf 70/30 16 120 14.0 24.5 Mixed under vacuum while heating from 85C to 105C. Hot plate cure 46/51 sec. 32 Ra Nf 70/30 2 200 14.2 32.63 Resins physically mixed 33 Ra Nf 70/30 5 19.7-21.8 17.5-22.4 Hot plate cure 55/60 sec. 34 Ra Nf 70/30 4 180 12.5-15.0 22.2-23.8 35 Ra Nf 70/30 0.1 440 235-25.] 25.65-12.33 Resins physically mixed 36 Ra Nf 70/30 0.05 440 27.4 15.67 Resins physically mixed 37 Ra Nf 70/30 5 min. 600F 23.6 19.45 Resins physically mixed 38 Ra Nf 70/30 6 min. 600F 24.8 17.76 Resins physically mixed 39 Ra Nf 70/30 7 min. 600F 25.1 17.47 Resins physically mixed 40 Ra Nf 70/30 8 min. 600F 24.4 15.62 Resins physically mixed 41 Ra Nf- 70/30 10 min 600F 24.0 15.09 Resins physically mixed 42 Rg Nf 70/30 3 min 600F 22.5 5.45 Resins physically mixed 43 Rg Nf 70/30 2 min 600F 23.3 10.34 Resins physically mixed 44 Rg N1 70/30 4 min 600F 22.0 7.61 Resins physically mixed 45 Rg Nf 711/30 5 min 600"} 21.6 7.02 Resins physically mixed 46 Rg N1- 70/30 8 min 00l'- 21.) 4.81 Resins physically mixed Experiments 28-35 were tested for volatile loss at 600F for 2 hours and acetone extractable for 16 hours (ASTM D-494-46).

Experiments 36-46 were tested for volatile loss at 700F for 1 hour and acetone extractable for4 hours (ASTM D-494-46).

TABLE IV Oxyalkylated Percent Percent Example Resole Novolac Resin Volatile Acetone Hot Plate Behavior Number Formulation Formulation Formulation Ratio Loss Extractable At 500F 47 Rg Rj 70/30 21.19 15.83 Slight smoke-very slight softening 48 Rf Rj 70/30 31.71 0.11 Smoky softens odor -oily appearance slight caking 49 Rg & Rf Rj 35/35/30 26.28 31.47 Smoky slight softening odor 50 Rg & Rh Rj 35/35/30 22.77 24.05 Slight smoke slight softening slight odor Oxalic Acid TABLE [V Continued Oxyalkylated Percent Percent Example Resole Novolac Resin Volatile Acetone Hot Plate Behavior Number Formulation Formulation Formulation Ratio Loss Extractable At 500F 51 Rg Nd Rj /15/70 14.43 15124 Smoky softens 0d0roily cakes 52 Rg Nb Rj 70/15/15 I 1.57 0.89 Very slight smoke very slight softening 53 Rg & Rf /40 10.51 0.97 No smoke very slight softening 54 Rf N1 80/20 20.13 32.99 Smoky slight softening odor -oily 55 Rg & Rf Nf 40/40/20 16.51 6.59 Slight smoke slight softening 56 Rg & Rh Nf 35/35/30 17188 13.50 Slight smoke very slight softening 57 Rg Nd Nf /10/20 13167 7.30 Slight smoke softens very oily cakes 58 Rg Nb Nf 70/10/20 12.26 0.32 No smoke slight softening 59 Rf& Ri 60/40 10.92 15.96 Slight smoke softens slightly oily slight caking 60 Rf Nd /20 12.56 18.58 Slight smoke slight softening slightly oily 61 Rf 8L Rg Nd 20/70/10 9.18 7.01 Smoky softens oily slight caking 62 Cardolite NC-104-20 Cashew Nut Shell Oil Friction Particles Smoky very slight softening slight odor TABLE V Resole Resin Formulations Resin a b c d e f g h 1 Raw Material:

Acetic Acid 0.18 0.04 Alcohol 23-90 Ammoniacol Liquor 0.711 2.43 Aniline 4.86 Casein l-ftfi Caustic Soda 0.15 0.38 0136 0.17 2.14 Citric Acid Deodorant Formaldehyde (37.2%) 47.36 54.41 49.44 50.74 48.44 29.00 56.91 45.09 24.45 Hexamethylene tetraminc 1.18 Lime 0.71 0.81 Melamine (Buffered) 12131 Meta-Para Cresol 1.78 Methanol 1.65 Ortho Cresol 3.85 Oxalic Acid 0.24 0.02 Para-Tertiary Butyl 21.60

Phenol Para-Tertiary Octyl 19.93

Phenol Phenol 43.22 38.86 32.93 36.95 18.77 19.93 40.65 52.37 1000 Phosphoric Acid 0.61 Propylene Oxide 121.5 Sulfuric Acid 2,76 Triethylamine 7 2 Urea (Shotted) 7,72 Urea Formaldehyde 23.84 Water 1.51 1.16 15.57 0.63 1.63 0.48 27.77 Xylene 21.21

"in Rcsolc Rj, the phenol. formaldehyde and 2.5 parts of triethannlaminc were first reacted. This product is then oxypropylatcd with the remaining specified ingredients.

TABLE V1 Novolac Resin Formulations Resin a b c d e f g h Raw Material Ammoniacal Liquor 2.31 Aniline 43.92 Beta Naphthol 37.80 Butyl Acid Phosphate 0.02 Castor Oil 36.77 Caustic Soda Ethylene Oxide 36-63 Formaldehyde (37.2%) 6.67 40.62 54.32v 22.92 34.70 16.98 19.72 35.95 Furfural 3 lsobutyraldehyde 17-42 Lime 0.14 0.48 Limonene 19.19 Linseed Oil 24.26 Maleic Anhydride (W2 Sodium alkylaryl sulfonate 0.01 0.06 0.01 0.12 p-Octyl Phenol 73-95 TABLE VI Continued Novolac Resin Formulations Resin a b c d e f g h Raw Material Stearic Acid 1.10 Sulphuric Acid 0.08 0.88 0.6] Water 0.67 0.59 0.88 0.28 0.96 1.06 Xylene 5.58 Phenol 22.16 58.45 54.91 45.85 60.68 24.67

We claim: 2. The particle of claim I wherein the first said resole in the particle is the condensation product of phenol 1. A friction particle comprising a non-catalyzed and formaldehyde in an alkaline medium product of the rea ti n t about 225 to about 400 F 15 3. The friction particle of claim 1 which comprises of a non-hydroxy-alkylated, hydroxy aromatic hydrothe reaction product of about 95- to about 60 percent carbon-aldehyde resole containing substantially no ethy Weight of nowhydroxyulkylmedr non'alkylmed erified aromatic hydroxy] groups with an alkylated hy- 6 and abou 10 about 40 percent by weight of a droxy aromatic hydrocarbon-aldehyde resole, until the non'hydmxyalkylmedi alkylated resoleresulting product is substantially insoluble in acetone, A brake lining Comprising the cured ProducI of 11 infusible, and does not soften slightly under mechanical friction Pdrlicle of Claim 9 a resin binder and an inofforce at a temperature below 400 F. and has substanganlc fillertially no cohesive or bonding strength, wherein said A brake lining comprising the Cured Product of non-hydroxyalkylated resole comprises about 60 to about 30 I0 60 Weight Pe sbest s iber. up to about 95% of the weight of the r si components, about 40 weight percent of other inorganic fillers and wherein the alkylated groups are substituted on the ara ras bou 5 0 5 g t percent of the r ction omatic ring and are selected from the group consisting particle of claim I, and about 15 to weight percent of: of binder.

a. alkyl groups of l to 60 carbon atoms, 6. A brake lining comprising the cured product of b. cycloalkyl groups of5 to l2 carbon atoms, 30 about 30 to 60 weight percent asbestos fiber, up to 0. alkyl, aryl and cycloalkyl ketonic groups wherein about 40 weight percent of other inorganic fillers and the hydrocarbon portion is defined in (a) and abrasives, about 5 to 15 weight percent of a friction (b). particle of claim 3, and about l5 to 30 weight percent d. alkyl, aryl and cycloalkyl carboxylic groups of binder.

wherein the hydrocarbon portion is as defined in 7. The friction particle of claim 1 in which comprises (a) and (b), the reaction product of about 5 to about 95 percent by c. aryl groups of 6 to 24 carbon atoms, and weight of a non-hydroxyalkylated, alkylated resole and f..aryl substituted alkyl wherein the aryl is phenyl. about 95 to about 5 percent by weight of a different lower alkyl-substituted phenyl or hydroxy substinon-hydroxyalkylated, alkylated resole. tuted phenyl.

} UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,864,304 DATED February 4, 1975 INVENT0R(5) Frank S. Grazen et at His certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

At Column 3, Hne 61, for "comounds" read "compounds".

At Columns 11 and 12, in Table I, in Example Number 8, in the last column of the table, for "mess-soft" read "mass-soft".

Signed and sealed this 1st: day of July 1975.

fittest:

C, ZL- RRSI-LXLL DAB-IE3 ILL-la; C. UILDO; Commissioner of Patents :tttesting; Officer and Trademarks 

1. A FRICTION PARTICLE COMPRISING A NON-CATALYZED PRODUCT OF THE REACTION AT ABOUT 225* TO ABOUT 400*F. OF A NON-HYDROXYALKYLATED, HYDROXY AROMATIC HYDROCARBON-ALDEHYDE RESOLE CONTAINING SUBSTANTIALLY NO ETHERIFIED AROMATIC HYDROXYL GROUP WITH AN ALKYLATED HYDROXY AROMATIC HYDROCARBONALDEHYDE RESOLE, UNTIL THE RESULTING PRODUCT IS SUBSTANTIALLY INSOLUBLE IN ACETONE, INFUSIBLE, AND DOES NOT SOFTEN SLIGHTLY UNDER MECHANICAL FORCE AT A TEMPERATURE BELOW 400*F. AND HAS SUBSTANTIALLY NO COHESIVE OR BONDING STRENGTH, WHEREIN SAID NON-HYDROXYALKYLATED RESOLE COMPRIESE ABOUT 60 TO ABOUT 95% OF THE WEIGHT OF THE RESIN COMPONENTS, WHEREIN THE ALKYLATED GROUPS ARE SUBSTITUTED ON THE AROMATIC RING AND ARE SELECTED FROM THE GROUP CONSISTING OF: A. ALKYL GROUPS OF 1 TO 60 CARBON ATOMS, B. CYCLOALKYL GROUPS OF 5 TO 12 CARBON ATOMS, C. ALKYL, ARYL AND CYCLOALKYL KETONIC GROUPS WHEREIN THE HYDROCARBON PORTION IS AS DEFINED IN (A) AND (B), D. ALKYL, ARYL AND CYCLOALKYL CARBOXYLIC GROUPS WHEREIN THE HYDROCARBON PORTION IS AS DEFINED IN (A) AND (B), E. ARYL GROUPS OF 6 TO 24 CARBON ATOMS, AND F. ARYL SUBSTITUTED ALKYL WHEREIN THE ARYL IS PHENYL, LOWER ALKYL-SUBSTITUTED PHENYL OR HYDROXY SUBSTITUTED PHENYL.
 2. The particle of claim 1 wherein the first said resole in the particle is the condensation product of phenol and formaldehyde in an alkaline medium.
 3. The friction particle of claim 1 which comprises the reaction product of about 95 to about 60 percent by weight of a non-hydroxyalkylated, non-alkylated resole and about 5 to about 40 percent by weight of a non-hydroxyalkylated, alkylated resole.
 4. A brake lining comprising the cured product of a friction particle of claim 1, a resin binder and an inorganic filler.
 5. A brake lining comprising the cured product of about 30 to 60 weight percent asbestos fiber, up to about 40 weight percent of other inorganic fillers and abrasives, about 5 to 15 weight percent of the friction particle of claim 1, and about 15 to 30 weight percent of binder.
 6. A brake lining comprising the cured product of about 30 to 60 weight percent asbestos fiber, up to about 40 weight percent of other inorganic fillers and abrasives, about 5 to 15 weight percent of a friction particle of claim 3, and about 15 to 30 weight percent of bindEr.
 7. The friction particle of claim 1 in which comprises the reaction product of about 5 to about 95 percent by weight of a non-hydroxyalkylated, alkylated resole and about 95 to about 5 percent by weight of a different non-hydroxyalkylated, alkylated resole. 